Process for manufacturing azodyestuffs



Patented Sept. 20, 1932 UNITED, STATES PATENT OFFICE;

rnoroLn LASKA, ARTHUR znscnm, wrnnum cnnrs'r, AND .ADOLF PETZOLD, or

OFFENBACH-ON-THE-HAIN, GERMANY, ASSIGNORS '10 GENERAL ANILINE WORKS,

INC., 01 NEW YORK, N. Y., A CORPORATION OF DELAWARE 'rnocnss non mmmac'runme AZODYES'IUFFS no Drawing. Application filed November 12, 1928, Serial No. 818,998, and .In Germany December 1a, 1e27.

' 'Our in entionrelates to a process for manufacturing azod'yestuf fs corresponding to the general formula, 1

twostbenzenenuclei may contain further substituents other than a sulfomc or carboxyl1c group and the benzene nucleus signified by II may be replaced by a naphthalene nucleus.

' abl inawhih formula X means an anion and the two benzene nuclei may contain further substitu'ents and the nucleus signified by II may v be replaced by a naphthalene nucleus, with a'Iiarylide of 2.3-hydroxynaphthoic acid and, a. inoeliminating the nitroso-group from the molecule of the azodyestufis formed: In this manner on the substratum applied dark violet to blue shades of an excellent fas'tness are obtained. The diazonitrosodlphenylamlne .Z.;f eompounds, which have not been used hitherto for the production ofazo-dy-estufi's insoluble in water, are distinguished by their particular capacity for combining and the stab lity of their solutions, a fact, which is of importance for producing ice colors by means of a standard bath. These diazonitrosodiphenylamine compounds are obtainable by the action of two molecular proportions of an alkali nitrite on one molecular proportion of an aminodiphenylamine compound inv a mineral acid solution.

The elimination of the nitrosogroup from the molecule of the primarily formedazodyestufl's is efiected by means of saponifying agents, such as alkalies or mineral or organic acids, advantageously with addition of a rein formula the naphthalene and the.

ducing agent such as hydrosulfites, dextrose,

"effect of a saponifying and of a reducing agent. "Advantageously one may add [an 1 emulsifying agent such as soap to the alkaline saponifying bath.

Suitable for the present process are nitroof -aminodiphenyl- Y sodiazo compounds amine itself and of its substitution products, such as 4-amino-2-methyldiphenylamine, 4-

amine-2-methoxydiphenylarmne, 4-amino-..

2"-ethoxydiphenylamine, 4 amino 2-pheno'xydiphenylamine, 4-amino-2-chlorodiphenylamine, 4-amino-3'-methyldiphenylamine, 4-amino-3-chlorodiphenylamine, 4-amino- 4-methyldiphenylamine, 4-amino-4-methoxydiphenylamine, 4 amino 4 ethoxydiphenylamine, 4-a'mino-4-phenoxydiphenylamine, 4-amino-4'-chlorodiphenylamine, 4-

amino.- 3 methyl-ff-methoxydiphenylamine, 4 amino 3' methyl 6' methoxydiphenylamine, 4-amino-2-methylr4'-chlorodiphenylamine, 4-amino-2-methyl-5'-ch1orodiphenylamine, 4-amino-3'-methyl6-chlorodiphenylamine, 4-amino-4'-methyl-3-chl0rodiphenylamine, 4=amino-2'-methoxy-4'-chlorodiphenylamine, 4 aminof- .3'.4-- dichlo'rodiphenylamine and 4-aminophenyl fl-naphthylamine.

As azocomponents there may be used for instance the 2.3-hydroxynaphthoylderivatives of aniline, of toluidines, of aminoethylbenzene,-of the alkyl-, aralkyland aryleth- .ers of aminophenols, of aminophenylketones,

-sulfones and sulfamines, of the halogensubstitution products of the aforesaid compounds, of naphthylamines and their derivatives, of arylenediamines, diaminodiaryls and their derlvatives, diamines, in which two arylresidues are united by a further complex, further such arylamides of 2.3-hydroxynaphthoic acid containing further substituents with the exception of sulfonic or carboxylic acid groups in the hydroxynaphthoylresidue such as .arylamides of 6-bromo-2.3 -hydroxynaphthoic acid. The dyestufi' formation may be carried out in an acid neutral or alkaline solution. For dyeing cotton goods by means of a standard bath it is of an ad-' vantage to use neutral nitrosodiazosolutions and to add to these solutions agents, which are suitable to neutralize the caustic alkali solution present in the paddling solution of the arylides of 2.3-hydroxynaphthoic acid,

such as magnesium or zinc sulfate.

3 21,4 parts of 4-amino-4'-methoxy-diphenylamine are diazotized in the usual man'- ner with 57 parts of hydrochloric acid 20 B and 15,2 parts of sodium nitrite at about 510,- whereby simultaneously a nitrosogroup is introduced. The free mineral acid is nearly neutralized with sodium acetate and the solution of the 4-methoxy-N-nitrosodiphenylamine--diazonium chloride thus obtained -is allowed to run at about 510 into a suspension obtained by dissolving 26,3 parts of the anilide of 2.3-hydroxynaphthoic acid in a sufficient quantity of a caustic soda solution with the addition of Turkey red oil and 400 parts of water and precipitating the solution by adding acetic acid. When the combination is complete the dyestufi formed is filtered ofl" and-boiled for some time in form of a paste, without drying'the' separated dyestufii', with about 400 parts of a solution containing 3 gms. of' sodium sulfide cryst. in presence of an emulsifying agent such as 3 gms. of soap in the liter. In this manner a dark blue pigment dyestufl is obtained by splitting off the nitrosogroup. The dyestuff thus obtained corresponds probably to the formula:

Emample 2 6' s. of the anilide of 2.3-h drox na hthoi ii cid are well ground with ti cc. d f TEF- key red oil and 9 cc. of a caustic soda solution of 34 B and they are dissolvedby adding 90 cc. of boiling water, then 90 cc. of cold water and at about 45 C. 600. of formaldehyde of 33% are added. After 5 to 10 minutes the whole is made up with cold water to 1 liter of liquor.

Cotton yarnis handled at about 30 for half an hour in this padding solution, centrifugated and then developed in the following bath:

2,24 gms. of -amino-diphenylamine sulfate are mixed with 10 cc. of hot water and for half an hour at about 90 in a bath containing 3 gms. of soap, 3 gms. of calcinated carbonate of soda and 3 gms. of cryst.v sodium sulfide in the liter, well rinsed and dried. The dyestufi thus produced corresponds probably to the formula:

A beautiful blue dyeing of an excellent fastness is thus obtained.

Ewample 3 with a solution containing 4 gms. of 2.3- hydroxynaphthoyl-el-chloroaniline, 10 cc. of Turkey red oil and 8 cc. of a caustic soda solution of 34 B in the liter and well wrung out. 22,8 gms. of l-aminoy-ethoxydiphe,

nylamine are diazotized with addition of a suflicient amount of diluted hydrochloric acid and 14 gms. of sodium nitrite, simultaneously the nitrosocompound being formed, and the liquor of diazotization is diluted until a concentration of .a hundredth mole of diazocompound in the liter.

-To this solution of 4-diazo-4J-ethoxy-N- nitrosodiphenylamine an amount of sodium bicarbonate until an almost neutral reaction is added and the impregnated cotton yarn is developed therein, then cold and hot rinsed.

When treating this dyeing thereafter at 8085 with a liquor containing 5 gms. of carbonate of'soda, 3 gms. of soap and 0,5 gms. of (anhydrous) sodium sulfide in the liter, and then rinsing and drying it as usually a navy blue dyeing of an excellent fastness is obtained. The dyestuff thus produced on the fiber corresponds probably to the formula:

OzHsOONO-N;

- v '95 Well boiled cotton yarn is impregnated described in Example 3 with 14 gms. of sodiumnitrite and the solution of the N-nitroso- 4'-methoxydiphenylamine-4-diazonium chlo.

.ride is made up until a concentration of 1 hundredth mole of 'the diazocompound in the liter.

When developing the padded cotton yarn with this N-nitroso-diazosolution neutralized with carbonate of calcium and treating it at about 90 for a quarter of an hour with a so-' lution containing 10 gms. of carbonate of soda and 2 gms. of dextrose in the liter, a blue-dyeing of the dyestufi' probably to the formula:

I no CHaONH-OC is obtained.

By. using 2.3-hydroxynaphthoyl-B-naphthylamine a somewhat more reddish blue dyeing is obtained.

' Emamplefi Woolen muslin is impregnated with a solution containing 5 gm's. of 2.3-hydroxynaphthoyl-4-toluidine, 5 cc. of Turkey red oil and 7,5 cc. of a caustic soda solution of 34 B6 in the liter, centrifugated and intermediately rinsed for 5-10 minutes with a solution containing 30 gms. of common salt 1n the liter, and then again well dehydrated.

The material is developed with a solution containing a hundredth mole of 4-diazo-4'- ethoxy-N-nitroso-diphenylamine in the liter and additioned with sodium acetate and after soaping at about 45 it is treated for about 15 minutes with a boiling liquor containing 3 cc. of formic acid of 90% in the liter. In this manner a blue dyeing is obtained. The dyestufi' fixed thereby on the fiber corresponds probably to the formula:

Example 6 3' gins. of 2.3-hydroxynaphthoyl-4-toluidine are dissolved with 6 cc. of a caustic soda solution of 34 B and 3 cc. of Turkey red I oil with addition of 3 cc. of formaldehydeof 33% and of one of the usual protective agents,

e. g. 3 gms. of Protectol I double powder (of.

corresponding Colour Index 1924, page 363) to one liter of a adding solutio ilk yarn is impregnated with this solution at about 25 for a quarter of an hour, then 10 gms. ofcommon salt are added per liter. of liquor and the yarn is handled for about a quarter of an hour and well dehydrated.

'It is developed in a bath neutralized with sodium acetate and containing an amount of dlazonitrosocompound corresponding to 1,25 gms. ofg4-amino-4-methoxy-diphenylamine after addition of 5 co. of an acetic acid of 50% and 10 gms. of common salt per liter.

' Then the silk am is well rinsed and treated thereafter wlth a boiling liquor containing 0,5 gms. of (anhydrous) sodium sulfide, 2 gms. of carbonate of soda, 3 gmsof soap and 0,5 gms. of Protectol I double powder in the liter, well rinsed in the cold and dried.

A clear blue dyein is obtained. The dyestufi' thus fixed is i entical with the dyestufi obtained according to Example Example 9 v trifugated and then developed in the follow,-

ing bath: 1

2,65 gms. of 4-amino-4'--methoxydiphenylamine sulfate are mixed with 10 cc. of hot water and 3 cc. of hydrochloric acid of 20 B, then 50 cc. of ice water and 1,42 gms. of sodiumnitrite are. added and the mass is allowed tov stand for half an hour while stirring. Then 2,5 gms. of magnesium sulfate or the corresponding amount of zinc sulfate dissolved in water and 1 gm. of sodium bicarbonate are added and the whole is made up with cold water to 1 liter of liquor.

The padded material is treated in this developing solution for half an hour and well rinsed.

Then .the well rinsed dye-goods are treat/ed for half an hour at about in a bath containing 3 guns. of'soap, 3 gms. of calcinated carbonate orxsoda and 3 gms. of cryst. sodium sulfide in the liter, well rinsed and dried. The dye-stuff thus produced corresponds probably to the formula:

are dissolved by A beautiful blue dyeing of an excellent fastness is thus obtained.

Ezmmple 8 1. Padding solution:

7 gms. of 2.3-hydroxynaphthoyl-2-toluidine are well ground with 10 cc. of Turkey red oil and 11 cc. of a caustic soda solution of 3l B and they are dissolved. by adding 105 gms. of boiling water and by boiling again the mass. Then 105 gms. of cold water and at about 50 C. 7 cc. of formaldehyde of 33% are added. After some minutes the whole is made up with cold water to 1 liter. 2. Developing bath:

2,63 gms. of 4-amino 4'-methoxydiphenylamine sulfate are stirred with 10 cc. of hot water and 3 cc. of hydrochloric acid of 20 B, then 50 gms. of ice-water and 1,42 gms. of sodium nitrite are added and the mass is allowed to stand for half an hour while stirring. Then 3 gms. of zinc sulfate dissolved in water and 1gm. of sodium bicarbonate are added and the nitrosodi'azosolution is made up with cold water to 1 liter.

The dye goods is impregnated with the aforesaid padding solution for half an hour,

1 centrifugated and developed at about 10 in the aforesaid developing bath for half an hour, well rinsed and thereafter treated with a bath containing soap, carbonate of soda and sodium sulfide, as described in the foregoing examples.

Injythis manner a beautiful greenish blue dyeiiig of an excellent fastness is obtained. 'lheydyest-ufi thus fixed on the fiber corresponds probably to the formula:

padding-machine with a liquor prepared as follows: i

15 gms. of 2.3-hydroxynaphthoyl-4-chl0ro aniline are mixed with 20 cc. of Turkey red oil and 24 cc. of a caustic soda solution of 34 B. The paste is dissolved to a clear solution by adding about 250 cc. of boiling soft water and made up with cold Water to 1 liter. Thectemperature of impregnation is 30- 35 Development The well squeezed piece goods, which are intermediately dried in a given case, are developed on the slop-padding machine by passing through a'bath of the following composition:

16 gms. of 4-amino-4'-methoxydiphenylamine are stirred with 25 cc. of hydrochloric acid of 20 B. and hot water and then diluted with about 500 cc. of cold water and a solution of 8,5 gms. of sodium nitrite in 50 cc. of water is added while stirring. After allowing to stand for half an hour the mass is filtered, the excess of mineral acid is nearly neutralized with 15 gms. of sodium acetate and the whole is made up with cold water to 1 liter. The temperature of development is about 15 C. Subsequent treatment: The piece goods are well rinsed'in the cold and are allowed to pass on the open washer through a boiling liquor, containing 5 gms. of sodium sulfide, 3 gms. of soap and 52 gms. of sodium carbonate in the liter. Then the piece goods is rinsed in a hot and a cold bath.

In this manner a blue dyeing of an excellent fastness'is obtained, the produced dyestufl' corresponding probably to the formula:

II Q O O O H0 H0 oxONH-oo on, x In the following table there are cited some Ewampleg further components suitable for the combination according to our process and the P dd ng; shades of dyeings obtained by the produc- The cotton-piece 1s padded on the slopnon of the dyestuffs on the fiber:

Diazo-nltroso-compound'of Combined with ggggggg 4-aminodiphenylamine 2.3-hydroxynaphthbyl-2-chloroaniline Dark blue D 2.3-hydroxynaphthoyl-4-chloroaniline Do. D 2.3-hydroxynaphthoyl-zphenetidine D0. D0, 2.3-hydroxynaphthoyl-l-naphthylamine Do. D 2.3-hydroxynaphthoyl-4-chloro-2anisidino Reddish dark blue D0 2.3-l1ydroxynaphthoyl-5-chlor0-2-anisidine Navy blue D 2.3-11ydroxynaphthoyl-2-aminodiplienyl-ether Blue 1) 2. 3-hydroxynaphthoyl-i-emmo-plreny]-benzy1-ether Reddlsh blue di-(2.3-hydroxynaphthoyl) 4.4'- diammo- 2.2.5.5 tetrachloro- Navy blue '7 diphenylurea bis-2.3-hydroxynaphthoyl dianisidine Dark violet 4-amino-2-methyldiphenylamine 2.3-hydroxynaphthoyl-anunohydroquinonedimethylether Reddish navy blue 2.3-hydroxynaphthoyl-5-chloro-2-anisidine Dark navy blue D 2.3-hydroxynaphthoyl-2-am1no-3-naphtholmethylether Dark reddish Navy ue 4-amino-2-methoxydiphenylamine 2.3-hydroxynaphthoyl-4-toluidine Dark violet. Do 2.3-hydroxynaphthoyl-EI-phenetidine Do. 2.3-hydtoxynaphthoyl-2-naphthylamine D0. 2.3-hydroxynaphthoyI-Z'ammoethyI-benzeno Do.

Shade of dyeln Dlaze-nltroeocompwnd 0! Combined with obtained 7 V E De. 2.3-hydroxynepbthoy -2-emlno-3- hthel-methylether Black-blue. 4-amlno-2'-ethoxydiphenylamlne 2.3-bydroxynapbthoy Miami d5. Dark blue Do. 2.3-hydroxynaphthoy am ahthylamine Do. Do. za-hydroxynephjhey +0 oro-z-anleldlne Navy blue Do, 2.3-hydroxyneglfthey -2-emln0-4-chloro-1-ethylbenzene Dark blue 4-nmlno-2-phenoxydlphenylamlne 2.3-b dm e- +toluidine Dark navy blue Do. 2.3-hydroxyziephthoy -2-phenetldlne Reddish navy blue Do. 2.3-hydroxynaphthoy -3-ehleroanll1ue Navy blue 4-amlno-2'-chlol'odlpbenylemlne 2.3-hydroxynaphthoy -3-nltroenillne ark blue DO- 2.3-5: dIU,l-llipht..l0 +eh1m'0enfllne RQddlSh navy blue Do. 2.3hydroxynaphtaoy -4-amlno-1-ethylbenz n Do, Do. 2.3-hydroxynaphthoy -1-ne hthylamlne Do, 4-amino-3-methyldlphenylemlne 2.3-hydroxynapht boy -2-ch oxoenillue Do. o. 2.3-hydr0xynapht boy -5-0hloro-2-anlaldlne Do. 4-mino-3"chlotodlpheuylamlne 2.3-hydroxynapbtboy -3-toluidlne New blue no. V 2.3-hydroxynephthoyl-z-phenetldlne Do. Do. 2.a hydroxynaphthoyl-Z-amlno-tl-naphthol-methylether Black violet 4-emlno-4-methyldlphenyla nlne 2.3-hydroxynaphthoyl-4-toluldine Reddlsh d k l D V 2.3-1:ydroxynephthoyl-4-chloroenillne Redd navy blu Do. 2.3-hydroxynephthoyl-lS-ehloro-Z-toluldlne 0. Do. 2.3-1:ydroxynaphthoyl-Z-ggyhthylamlne Do. 4-amiuo-4-methoxydiphenylemlne 2.3-hydroxynaphthoy -2- sidine Dark blue Do. 2.3-hydroxynaphthoy +anlsldine Do. Do. 2.3-hydroxynaphthoy -3ehl0roanillne Do. Do. 2.3-hydroxynaphthoyl-5-chloro-2-toluldlne Blue Do. 2.3-hydroxynaphthoyl-50l11oro-2-anlsldine Dark blue Do. 2.3-hydroxynaphthoyl-2-naphthylamlne Reddlsh navy blue Do. 2.3-hydroxynaphthoyl-3-ammoacetophenone reenlsh blue Do. 2.3 hydroxynaphthoyl 3 amino 4 methoxybenzene -sulefonic ac1d-d1metl1ylamlde Do. 2.3-):ydroxynaphthoyl-Z-amlno-tolyl-d-ethyl-mlfone teenlsh blue Do. 6-br0m0-2.3-hydroxynaphthoyl-anjllne Dark blue Do. e-bmme-2.s-hyd y p oyl-schlom-aaulsldln Dark na blue 4-amino-4-ethoxydiphenylamlne 2.3-hydroxynaphthoyl-anlhne I Greenlsh lue Do. 2.3-.hydroxynaphthoyl-2-toluidine Dark blue Do. ,2.3-hydroxynephthoyl-B-toluldine Do. Do. 2.3- hydroxyna hthoyl-4-amsldlne Do. Do. 2.3-hydroxy'nap thoyl-s-ehloroenillne Greeuisb blue Do. 2.3-11ydroxynephthoyl-Z-nephthylamlm Reddlsh navy blue Do. 6-bromo-2.3hydroxynaphthoyl-2-anisidine Reddlsh dark blue Do. 6-br0mo-2.3-hydr0xynaphthoyl-Lnaphthylamine Greem'sh blue Do. dl-(2.3-hydroxynaphthoyl)-2.5-diamino-#methoxy-l-toluene N W Blue Do. dl-(2ill-hygroxynephthoyl-MA diamino 2.2- dlmethyl dipherk l e ny me ane Do. dl-(2,3-hydroxynaphth0yl) ifl-dlaminobenzophenone Greenlsh blue 4-amlno4-chlorodlphenylamine 2.3-11ydroxynaphthoyl-z-an sldine Reddlsh navy blue Do. 2.3-hydroxynaphthoyl-4-amsidine Do. Do. 2.3-hydroxynaphthoyl-5-chloro-2-anlsldine Do. Do. 2.3-hydroxynaphthoyl-Mmphthylamine Do. Do. 2.3-1:ydroxynaphthoyl-Z-ammo-B-naphtholmethylethet 4-emino4-phenoxydiphenylamine 2.3-hydroxynaphthoyl-4-phenetidine Reddlsh dark blue Do. 2.3-hydroxynaphthoyl-4-ch1oroaniline Do. Do. 2.3-1:ydroxynaphthoyl-l-uaphthylemine Do. 4-amino-3-methyl 4-methoxydiphenylamine 2.3-1)ydroxynaphthoyl-amline Blue Do. 2.3-hydroxynaphthoyl-4-ehloroanfllne Dark blue Do. 2.3-hydi-oxynaphthoyl-2-naphthylamlne Reddlsh navy blue D o. 2.3-hydroxynaphthoyl-4-amsidine Dark blue Do. 2.3-hydroxynephthoyl-2-toluldine Do. Do. 2.3-hydroxynaphthoyl-2-chloroanillne Reddlsh dark blue Do. 2.3-hydroxynaphthoyl-a-chloroaniline Dark blue 4-amino-3-methyl-6-methoxy-dlphenylamlne 2.3-hydroxynaphthoyl-3-toluidine Do.

Do. 2.a hydroxyuaphthoyl-5-chloro-2-anlsidlne 7 Navy blue Do. 2.3-hydroxynaphthoyl-l-naphthylanfine Dark blue 4-amiuo-2-metbyl-4-chloro-diphenylamine 2.3-hydroxynaphthoyl-3-toluidine Navy blue Do. l 2,3-hydroxynaphtl1oyl-3-nitroaniline Dark vlolet Do. 2.3-hydroxynaphthoyl-aminqhydroquinonedimethylether Reddlsh navy blue 4-amin0-2-rnethyl-5-chloro-diphenylamine 2.3-l1ydroxynaphthoyll-toluldine I Do. Do. 2,3-hydroxynaphtheyl-l-naphthylamine Do. Do. 2.3-hydroxynephthoyl-8-naphthylamjne Do. 4-amino-3-methyl-6-chloro-dlphenylamine 2.3-hydr0xynaphth0y1-5-0hl0r0-2anisidine Derkylolet Do 2.3-hydroxynaphth0yl-2-8min04-chloro-1-ethylbenzene Reddlsh navy blue D0 2.3-hydorxynaphthoyLl-naphthyamine a blue 4-amino-4-methyl-3-chloro-diphenylamine 2.3-l1ydr0xynaphth0yl-aniline Reddlsh navy blue Do. 2.3-hydroxynephthoyl-Z-toluidine Do. D 2.3-hydroxynaphthoyl-4-tqluidine Do. 4-amlno-2-methoxy-4'-chloro-diphenylamine 2.3-hydroxynaphthoyl-ammohydroquinonedimethylether D rk vl D0 1 2.3-hydr0xynaphthoyl-2-naphthylamine Dark navy blue 2.3hydroxynaphthoyl-Z-amiuo-3-naphthol-methylether N 3 W D1118 4 gimlilno i3 lnethoxy 6.2- dimethyl 4'- ehloro 2.3-hydroxynaphthoyl-p-chloroaniline Violet p eny 51111119 Do. 2.3-hydroxynaphthoyl-Zmaphthylamine Do. 4-amino-3.4'-dichlorodlphenylamine 2.s-hydroxynaphthoyl-aniline Dark violet 2.3-hydroxynaphthoyl-3-toluidine Do. 2.3-hydroxynaphthoyl-S-anisidine Black violet 4-amino-phenyl-fl-naphthylamine 2.3-hydroxynaphthoyl-aniline ue 2.a-hydroxynephthoyl-p-anisidine Reddlsh dark blue 2. -hydrexynaphthoyl-m-chloroaniline o. 4-amino-3.2'-dimethoxy-diphenylamine 2.3-bydroxynaphthoyl-l-naphthylamine Reddlsh blue D0- 2.a-hydroxynaphtboyl-2-naphthylamine D0. 0- 2.3-]:ydroxynaphthoyl-4-chloroaniline a Do- Do. 2.3-11ydroxynephthoyl-5-chloro-2-toluidine Do. Do. 2.3-hydroxynaphthoyl-eminohydroquinouedlmethylether D0. 4-amlno-3.2-dlmetl1yldiphenylamlne 2.3-hydroxynaphthoyl-aniline Reddlsh dark blue Do. 2.3-hydr0xynaphthoyl-2naphthylamlne D0. D0. 2.3-hydroxynaphthoyl-Z-toluidine Do. Do. 2.3-hydroxynaphthoyl-z-enjsidine D0. 2.3-hydroxynaphthoyl-4-chloroaniline Do. 4-amino-3.2-dlcblorediphenylamine 2.3-hydroxynaphthoybaniline Dark vlolet Do. 2.3-hydroxynaphthoyl-Z-naphthylamine Do. I Do. 2.3-hydroxynaphthoyl-5-ch1oro-2-toluidine D0.

Do. 2.3-hydroxynanhthoyl-aminohydroquinonedimethylether Reddlsh dark violet The dyestuffs being object of the present ing process according to one of the usual invention can be also produced by the printmethods, it being possible-t0 eliminate the nitrosogroup from the molecule of the dyestuffs by the steaming process.

The blue dyeings obtainable according to the present process are distinguished by an excellent ability of being discharged.

In the following claims we understand under the combining process the combination of the components in substance as well as upon a substratum, particularly on the fiber.

Ve claim:

1. A process which comprises combining an N nitrosodiphenylamine 4 diazonium salt of the general formula:

in which formula X means the acid residue of the salt and the two benzene nuclei may contain halogen-, alkyl-, oxalkylor oxarylgroups, with an arylamide of 2.3-hydroxynaphthoic acid, the aryl residue of which is of the benzene or naphthalene series and the naphthalene nucleus of which may contain,

a halogen, and splitting off the nitrosogroup. from the molecule of the azodyestufis thus formed. .7

2. A process which comprises combining an N nitrosodiphenylamine 4 diazonium salt of the general formulas in which formula X means the acid residue of the salt and the two benzene nuclei may contain halogen-, alkyl-., oxalkylor oxarylgroups, with an arylamide of 2.3-hydroxynaphthoic acid, the aryl residue of which is of the benzene or naphthalene series and the naphthalene nucleus of which may contain a halogen, and splitting off the nitrosogroup from the molecule of the azodyestufis thus formed by treating them with saponifying agents;

3. A process which comprises combining an N nitrosodiphenylamine 4 diazonium salt of the general formula:

agents in the presence of a reducing agent.

4. A process which comprises combining an N nitrosodiphenylamine 4 diazonium salt of the general formula:

in which formula X means the acid residue of the salt and the two benzene nuclei may contain halogen-, alkyl-, oxalkylor oxarylgroups, with an arylamide of 2.3-hydroxynaphthoic acid, the aryl residue of which is of the benzene or naphthalene series and the naphthalene nucleus'of which may contain a halogen, and splitting off the nitrosogroup from the molecule of the azodyestuffs thus formed by treating them with saponifying agents in the presence of a reducing and an emulsifying agent.

5. A process which comprises combining an N nitrosodiphenylamine 4 diazonium salt of the general formula:

halogen, and splitting off the nitrosogroupfrom the molecule of the azodyestufl's thus formed by treating them with an alkali metal sulfide solution.

6. A process which comprises combining an N nitrosodiphenylamine 4 diazonium salt of the general formula:

v No Y I Q NPX.

in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, and the two benzene nuclei may contain further substituents of the same grouping, with an arylamine of 2.3-hydroxynaphthoic acid, the aryl residue of which is of the henzene or naphthalene series and the naphthalene nucleus of which may contain a halogen, and splitting off the nitrosogroup from the molecule of the azodyestuffs thus formed.

7. A process which comprises combining an N-nitroso-diphenylamine4-diazonium salt of the general formula:

in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and thoic acid, the aryl residue of which is of the benzene or naphthalene series'and the naphthalene nucleus of which may contain a halogen, and splitting off the nitrosogrou from the molecule of the azodyestufis thus ormed by treating them with saponifying agents.

8. A process which comprises combining an N-nitrosodiphenylamine-tdiazonium salt.

of the general formula:

IIIO

in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, and the two benzene nuclei may contain further substituents of the same grouping, with an arylamide of 2.3-hydroxynaphtholc acid, the aryl residue of which is of'the benzene or naphthalene series and the naphthalene nucleus of which maycontain a halogen, and splitting off the nitrosogroup from the molecule of the azodyestufi's thus formed by treating them with saponifying agents in the presence of a reducing agent.

' 9. A process whichwomprises combining an N-nitrosodiphenylaminel-diazonium salt of the general formula:

in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, and the two benzene nuclei may contain further substituents of the same grouping, with an arylamide of 2.3 h'ydroxynaphthoic acid, the aryl residue of which is of the benzene or naphthalene series and the naphin which formula X means the-acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, and the two benzene nuclei may contain fur"- ther substituents of the same grouping, with an arylamide of 2.3-hydroxynaphthoic acid, the aryl residue of which is of the benzene or naphthalene series and the naphthalene nucleus of which may contain a halogen, and splitting off the nitrosogroup from the molecule of the azodyestuffs thus formed by treating them with an alkali metal sulfide 'solution.

11. A process which comprises combining an N-nitrosodi henylam'ine-4-diazonium salt of the general ormula:

N0 YOItOM-X. in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

in which formula Z and Z; mean hydrogen,

halogen or an alkylor oxalkylgroup and splitting off the nitrosogroup from the inolecule of the azodyestufi's thus formed.

12. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the general formula:

in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

. 9 oo-nnO-z in which formula Z and Z mean hydrogen, halogen or an alkylor oxalkylgroup, and splitting off the nitrosogroup from the molecule of the azodyestufis thus formed bytreating them with saponifying agents.

13. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium. salt of the general formula:

in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

in which formula Z and X mean hydrogen, halogen or an alkylor 'oxalkylgroup, and splitting off the nitrosogroup from the molecule of-the azodyestufis thus formed by treating them with saponifying agents in the presence of a reducing agent. I

14;. A process which comprises combining an N-nitrosodiphenylamine--diazonium salt of the generalformula:

III 0 in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

'OH Z1 (JO-NHOZ:

in which formula Z and Z mean hydrogen, halogen or an alkylor oxalkylgroup, and

splitting ofi the nitrosobroup from the molecule of the a'zodyestuffs thus formed by treating them with saponifying agents in the presence of a reducing and an emulsifying agent.

15. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the general formula:

No a i M.

in which formula X means the acid residue of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl,

with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula 0 O-NHOZ:

r ro alkyl-OON-O-Nr-X wherein X means the acid residue of the salt with a phenylamideof 2.3-hydroxynaphthoic acid of the general formula:

in which formula Z and Z mean hydrogen, halogen or an alkylor oxalkylgroup, and splitting off the nitrosogroup from the molecule of the azodye'stuflfs thus formed.

17. A process which comprises combining an N-nitrosodiphenylamine-t-diazonium salt of the formula:

wherein X means the acid 1 idue of the salt with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

in which formula Z and Z mean hydrogen,-

halogen or an alkylor oxalkylgrou and splitting off the nitrosogroup from the molecule of the azodyestuffs thus formed by treating them with saponifying agents.

18. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the formula:

III 0 wherein X means the acid residue of the salt with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

in which formula Z and Z mean hydrogen,

halogen or an alkylor oxalkylgroup,'and splitting off the nitrosogroup from the molecule of the azodyestuffs thus formed by treating them with saponifying agents in the presence of a reducing agent.

19. A process which comprises combining an N-nitrosodiphenylaminei-diazonium salt of the formula:

IIIO

wherein means the acid residue of the salt with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

OH Q

-o O-NH-O ZL in which formula Z and Z mean hydrogen, halogen or an alkylor oxalkylgroup, and

splitting off the nitrosogroup from the molecule of the azodyestuffs thus formed by treating them withsaponifying agents in the presence of'a reducing and an emulsifying agent.

20. A process which comprises combining an N-nitrosodiphenylainine-47diazoniu1n salt of the formula:

III 0 wherein X means the acid residue of the salt with a phenylamide of 2.3-hydroxynaphthoic 1 acid of the general formula:

I of the formula:

wherein X means the acid residue of the salt, with a phenylamide of -2.3 -hydroxynaphthoic acid of the general formula:

in which formula Z and Z mean hydrogen, halogen or an alkylor oxalkylgroup, and splitting oif the nitrosogroup from the mole cule of the azodyes'tuffs thus formed.

22. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the formula:

V 1 10 a v v GHFO N M, wherein X means the acid residue of the salt,

with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula:

in which formula Z and Z mean hydrogen, halogen or an alkylor oxalkylgroup, and splitting off the nitros ogroup from the molecule of the azodyestuffs' thus formed by treating them with saponifying agents.

'23. A processwhich comprises combining of the formula: 7

wherein X means the acid residue of ,the salt,

with a phenylamide of 2.3-h'ydroxynaphthoic vacid of. the general formula:

in which formula Z1 and Z; mean hydrogen, f"v V ing them with saponifying agents in the presence of a reducing agent.

24L A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt I of the formula wherein X means the acid residue wherein X means the acid residue of the salt, with a henylamide of 2.3-hydroxynaphthoic acid 0 the general formula:

' on I F-CO-NH-OZ'L in which formula Z and Z mean hydrogen,

halogen or an alkylor oxalkylgroup, and splitting off the nitrosogroup from the molecule of the azodyestufi's thus formed by treating them with saponifying agents in the presence of a reducing and an emulsifying'agent, 25.'A process which comprises combining an N-nitroso'd1phenylaminel-diazonium salt of the formula i wherein X means the acid residue of the salt, with a phenylamide of 2.3-hydroxynaphthoic acid of the general formula V 7 in which formula Z and Z; mean hydrogen,

wherein X means the acidresidue of the salt, with a phenylamide of 2,3-hydr,oxynaphthoic acidlofthe 'formulaz s an N-nitrosodiphenylamine--diazonium salt i I wherein -Z means hydrogen or analliyl or "oxalkylgroup and splitting oifthe nitrosogroup from the molecule of the azodyestuffs thus formed.

27. A processwhich comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the formula:

salt, with y a phenylainide v of 2.3-hydroxy naphthoic acidofthe formula:

means hydrogen or 4 an alhyl or oxalkylg'roup, and splitting off the nitrosogroup from the molecule of the azodyestuifs thus formed by treating them with sapomfying agents.

28. A process which comprlses combining an N -nitrosodiphenylamine-4-diazonium salt of the formula:

wherein X means the acid residue of the salt, with a phenylamide of 2.3-hydroxynaphthoic acid of the formula:

wherein Z means hydrogen or an alkyl'- or oxalkylgroup, and splitting off the nitro sogroup from the molecule of the azodyestuffs thus formed by treating them with saponifying agents in the presence of a reducingagent.

29. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the formula:

wherein X means the acid residue of the salt, with a phenylamide of 2.3-hydroxynaphthoic acid of the formula:

wherein Z means hydrogen or an alkylor oxalkylgroup, and splitting off the nitrosogroup from the molecule of the azodyestufi's thus formed by treating them with saponifying agents in the presence of a reducing and an emulsifying agent.

30. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the formula:

III 0 wherein X means the acid residueof the salt, with a phenylamide of 2.3-hydroxynaphthoic acid of the formula:

wherein Z means hydrogen or an alkylor oxalkylgroup, and splitting oil the nitrosogroup from the molecule of the azodyestufisan N-nitrosodiphenylamine-4-diazonium salt of the formula:

wherein X means the acid residue of the salt, with 2.3-hydroxynaphthoic acid anilide and splitting off the nitrosogroup from the molecule of the azodyestufls thus formed.-

32. A process which comprises combining an N-nitrosodiphenylamine-4 diazonium salt of the formula wherein X means the acid residue of the salt, with 2.3-hydroxynaphthoic acid anilide and splitting off the nitrosogroup from the mole-- cule of the azodyestufls thus formedby treating them with saponifying agents.

33. A process which comprises combining an N-nitrosodiphenylamine--diazonium salt of the formula:

wherein X means the acid residue of the salt,

with 2.3-hydroxynaphthoic acid anilide and splitting ofl the nitrosogroup from the molecule of the azodyestuffs thus formed by treating them with saponifying agents in the presence of a reducing agent.

34. A process-which comprises combining an N-nitrosodiphenylamine-4-'diazonium salt of the formula:

wherein X means the acid residue of the salt, with 2.3-hydroxynaphthoic' acid anilide and splitting off the nitrosogroup from the molecule of the azodyestufi's thus formed by treating them with saponifying agents in the presence of a reducing and an emulsifying agent.

35. A process which comprises combining an N-nitrosodiphenylamine-4-diazonium salt of the formula:

thus formed by treating them with an alkali metal sulfide solution.

31. A process which comprises combining 

